EP2494344A1 - Feuchtigkeitssensor - Google Patents
FeuchtigkeitssensorInfo
- Publication number
- EP2494344A1 EP2494344A1 EP10795907A EP10795907A EP2494344A1 EP 2494344 A1 EP2494344 A1 EP 2494344A1 EP 10795907 A EP10795907 A EP 10795907A EP 10795907 A EP10795907 A EP 10795907A EP 2494344 A1 EP2494344 A1 EP 2494344A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- sensor
- carrier body
- substance
- salt
- humidity
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
- G01N27/22—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating capacitance
- G01N27/223—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating capacitance for determining moisture content, e.g. humidity
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
- A61B5/00—Measuring for diagnostic purposes; Identification of persons
- A61B5/44—Detecting, measuring or recording for evaluating the integumentary system, e.g. skin, hair or nails
- A61B5/441—Skin evaluation, e.g. for skin disorder diagnosis
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
- A61B2562/00—Details of sensors; Constructional details of sensor housings or probes; Accessories for sensors
- A61B2562/02—Details of sensors specially adapted for in-vivo measurements
- A61B2562/029—Humidity sensors
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/46—Wood
Definitions
- the invention relates to a sensor for determining moisture of materials, in particular of gases. Furthermore, the invention relates to a method for producing a sensor and / or a carrier body of a sensor for determining the moisture of materials. Such sensors and methods are used commercially in particular for determining the humidity in industrial applications.
- the invention can be advantageously applied in the field of transport of goods in the monitoring of the climate.
- the air humidity sensor can be used particularly advantageously in the determination of moisture of human or animal skin as well as in industrial and medical pharmaceutical applications.
- One method uses plastics, on which the moisture-water condenses, whereby the permittivity of the plastic or the condensate formed on the plastic changes and this change is measured by two electrodes arranged on the plastic. In particular, the capacitance between the two electrodes is determined.
- a major disadvantage of the plastic sensors is that they are not heat resistant, so ambient temperatures up to 70 ° C are possible, the absolute limit depending on the plastic is different at 100 ° C, otherwise irreversible strong deformations such as the fiber of the fiber composite occur, which lead to an aging of the layer. Even at lower temperatures, aging of the plastic occurs, so over time, the accuracy decreases due to the swelling of the plastics.
- the moisture absorption of the plastic itself is extremely low -1-3% by weight, whereby the deformation due to sources leads to significant irreversible changes.
- the plastic molecules change, so that an irretrievable change of the characteristic exists.
- the effect of UV radiation, heat lamps, sunlight, light bulbs, etc. also changes the plastic.
- the swelling or deformation irretrievably changes the characteristics of such a sensor element, so that meaningful and reproducible measurements can be made only at the beginning of the life of such a humidity sensor.
- an artificial aging of the component during production to achieve a lower sensitivity does not solve the problem described at the outset because the reaction rate decreases and aging effects only reduced, but not completely suppressed.
- the humidity that has been recorded in the course of a measurement can only be removed from the plastic extremely slowly, and in addition, the shape of the plastic is irretrievably changed.
- plastic sensors react extremely slowly because residual air moisture always remains inside. In particular, a reduction of the ambient humidity can be determined by such a sensor only with a very long time delay.
- the heating of the sensor which pursues the purpose of evaporating the water out of the plastic, is only conditionally possible, since heating the plastic to above 50 ° C already leads to irreversible changes in the behavior of the sensor, with a periodic heating / cooling to additional Fatigue of the plastic leads. Therefore, the sensors are subjected to targeted aging in order to take advantage of a more stable region that can be used in the area of short-lived consumer electronics.
- Current humidity sensors of this type are produced in so-called thin-film technology, with various plastics being used as the humidity-sensitive layer.
- the sensors are controlled by electrodes, whereby the humidity can be determined by the capacity of the sensor.
- the capacity or capacity change is evaluated and assigned to a predefined calibration function of humidity or humidity change.
- a fundamentally different type of air humidity sensor is lithium chloride thick-film sensors.
- Such sensors have a glass fabric into which the strongly hygroscopic salt lithium chloride is introduced.
- the lithium chloride reduces the water vapor pressure by about 90%, whereby strong water absorption up to a maximum of 400 grams per kilogram of water causes the substance only to appear in liquid hydrate form at low temperatures of below 98 ° C.
- a major disadvantage of lithium chloride is that it is chemically extremely reactive and corrosive, and that it damages even massive materials like concrete. Since lithium chloride is classified as hazardous, there is the additional problem of disposal of these sensors.
- the invention has for its object to overcome the problems mentioned above.
- the carrier body is made of or with an open-pore porous, humid-invariant, non-hygroscopic and high internal stiffness having support material, at least the pores of the carrier material with the moisture-water from the material used or standing in contact with the carrier material of the carrier body, or Gas or air space reversibly and reproducibly receiving and / or to the material or gas or air space donating substance, preferably with such an inorganic salt in dissolved, liquid, solid or crystalline form, filled or at least coated on their surfaces or walls are and that the conductance and / or electrical permittivity of said substance, in particular of the salt, the function of the humidity of the contacted with the thus acted support material of the carrier body in contact or standing material, in particular the humidity of the ambient air, reproducibly dependent.
- the substance is additionally arranged on the surface of the porous carrier material of the carrier body and is in material contact with the substance located in the pores of the carrier body or is of the same material.
- sodium chloride hardly reacts with its environment and even with direct contact with its environment no chemical reactions take place.
- the liquid lithium chloride is bound by the capillary action of the pores of the carrier body in the carrier body and does not drip. Since salts are distributed over a very small crystal lattice of e.g. 0.6nm, the smallest crack and unevenness in the pore of the material can be exploited in the crystallization and thus anchoring.
- an additional advantageous aspect of the invention provides that the inorganic salt in and on the support body is sodium chloride, ammonium dihydrogen phosphate, potassium nitrate, potassium chloride, sodium dicromate, lithium chloride, magnesium chloride, ammonium nitrate, magnesium nitrate or potassium carbonate or mixtures of salts.
- the carrier body consists of a material having open pores. The surface of the substance which is available for absorbing moisture-water from the ambient air thus becomes particularly large.
- a high- or dead-burned mineral oxide also has the advantage that the carrier body is subjected to only minor mechanical stresses due to moisture water stored in the substance.
- alumina, magnesium oxide or an open-pore foam or sintered metal is suitable.
- the carrier body and, if appropriate, the substance arranged in layer form on the surface of the carrier body are coated with a water-impermeable, but water vapor-permeable material, in particular Teflon.
- the humidity sensor can also be used for outdoor applications, especially in the rain.
- the carrier body a
- Printed circuit board material is present in the pores or etched surface or continuously or baked.
- Printed circuit board materials consist of different layers which are stacked, for example, in a laminate. The total thickness can only be 0.127mm due to the thinness of all layers.
- the last cover layer in a single-sided printed circuit board or the last thick layers in a two-sided printed circuit board or inner layers in multilayer printed circuit boards are usually made of copper, which is etched away, for example, and forms the printed conductors.
- the materials which are used below the copper as support layers or bodies or between the copper layers are suitable for integration of the inventive sensor are e.g.
- LTCC Low Temperature Cofired Ceramics
- HTCC High Temperature Cofired Ceramics
- moisture-resistant glasses titanium oxide, and combinations that allow no swelling and water retention in the carrier but only in the pores of the substrate. It may also contain additives which increase the internal stiffness, e.g. Glass fiber additives, etc. which are known in the art and cause no swelling.
- Other coatings below the sensor without contact with moisture may be any material, for example: plastics, thermoplastic polyimide (TPI), fluoropolymers (i.e., PTFE), polyester films.
- the carrier body consists of fiber-reinforced printed circuit board material, are etched in the pores on the surface.
- this sensor can be arranged directly on or in a printed circuit board of the above materials and thin alumina ceramic, so that the production of the sensor and the assembly of the Printed circuit board can be performed in a common manufacturing step.
- This allows a particularly simple production of the sensor and a sensor circuit, in particular an integrated RFID circuit.
- the electrodes pass through in the pores of the
- Carrier body embedded material are formed. This feature is particularly advantageous in combination with the use of printed circuit boards, in particular with the embodiment of the sensor as a via or above the printed circuit board, since the contacting can be carried out together with the production step of the board.
- a further preferred aspect of the invention provides that the carrier body and optionally the substance arranged in layers on the surface of the carrier body are coated with a water-impermeable, but water vapor-permeable material, in particular Teflon.
- a further preferred aspect of the invention provides that the carrier body consists of printed circuit board material in which the pores are superficially etched and / or, preferably with a laser, baked or the printed circuit board as such has pores.
- This development of the invention allows an alternative integration of a moisture sensor in a printed circuit board, wherein the additional manufacturing cost for the attachment of the moisture sensors is extremely low and thus the production cost can be greatly reduced.
- the electrodes are formed by embedded in the pores of the carrier body metal.
- the carrier body has a layer-like construction, and has at least one continuous macroscopic recess, which is at least superficially coated with the substance through the carrier body through the recess and the electrodes are arranged on, in particular opposite, sides of the carrier body , This allows easy production of a humidity sensor on a circuit board.
- a further particular embodiment of the invention provides that at least two electrodes are arranged in and / or on the carrier body or on the carrier material, which has a current flow and / or a charge shift at least in the substance, in particular in the salt, in the pores of the carrier material allow the carrier body and / or on the surface of the carrier body.
- This embodiment allows the use of low currents and voltage, which allows the use of the new sensors, especially in high-explosive atmospheres.
- this embodiment the displacement of salt ions in Avoiding the flow of current between the two electrodes, whereby the sensor is subject to very little aging effects.
- the electrodes are arranged superficially on the surface of the carrier body or of its carrier material, and that the substance is arranged in the pores of the carrier material, and optionally in the region between the two electrodes, wherein optionally the carrier material and at least one of the electrodes is at least partially covered with a layer of the substance on its surface.
- the formation of the electrodes is done in particular by evaporation or sputtering of the metal layer on the carrier body. It is particularly advantageous that the substance is arranged in the region between the two electrodes.
- the capacitance or conductance measured between the electrodes becomes very much dependent on the ambient air humidity.
- the carrier material and at least one of the electrodes are at least partially covered with a layer of the substance on its surface.
- this allows a particularly simple production and, furthermore, a particular strong dependence of the humidity on the conductance or the capacitance between the two electrodes is achieved.
- At least one of the electrodes itself binds the open-pore carrier material of the carrier body for the substance.
- conductive porous materials can be used, whereby an additional vapor deposition or sputtering step for creating the electrodes can be dispensed with.
- the electrodes extend into or pass through the carrier body, wherein the substance-coated or filled pores of the carrier body are arranged in the region between the electrodes, so that a current flow and / or a charge displacement between them is made possible.
- This allows particularly strong dependencies of the measured capacitance or conductance between the two electrodes on the respective prevailing humidity.
- a particularly large conductance or capacitance is achieved, wherein the dependence of the conductance or capacitance between the two electrodes is highly dependent on the humidity of the environment of the air.
- Another aspect of the invention provides that it means for heating and / or
- Cooling of the substance in particular a heating resistor or a Peltier element, which or preferably preferably rests flat on the carrier body.
- the substance can be dried very quickly by heat, which is a particularly rapid Response of the sensor to the respective humidity results.
- a subsequent cooling in particular by a Peltier element, the speed of the humidity sensor can be further increased by the temperature is lowered before the start of the measurement.
- a condensate which penetrates into the substance and causes a change in the capacitance or conductance between the two electrodes is formed. Thanks to these two measures, sensor response times of less than one second are possible.
- a further preferred embodiment of the sensor according to the invention provides that at least one, in particular doped, semiconductor layer is provided, which is electrically connected to the carrier body, wherein the carrier body acts in particular as a base layer of a bipolar transistor.
- the gain of the transistor depends very much on the ambient humidity, whereby the energy used for the measurement or the voltage used for the measurement can be further reduced. Furthermore, it can be provided that an antenna arrangement, in particular an RFID antenna, is arranged on the surface of the carrier body, which is at least partially covered or coated with the substance. In this way, the resonance frequency of the RFID tag is changed, whereby selectively those RFID Tag can be addressed by selecting the frequency, which are surrounded by air with a given humidity.
- a further preferred embodiment of the invention provides that a capacitor connected in parallel with the antenna is coated on its surface with the substance, wherein the substance with another contact forms a capacitance parallel to the antenna for energy storage of the energy transmitted by the RFID transmitter a digital transmitting unit is provided for transmitting digital transmission signals that drives the antenna.
- the substance is a salt mixture and a
- the substance contains a proportion of 0.002 to 0.08% by weight of bromide ions. It can also be provided that the substance has a share of 0.0001. to 0.006 wt% iron ions.
- the substance contains a proportion of 0.001 to 0.06% by weight of calcium ions.
- Calcium ions can be added to the salt mixture and serve as a drying agent and provide the stability and strength of the salt crystal in the pores.
- the substance contains a proportion of 0.0007 to 0.02% by weight of sulfate ions. Furthermore, it can be provided that the substance contains a proportion of 0.0004 to 0.04% by weight of barium ions. It can also be provided that the
- Substance contains a proportion of 0.0004 to 0.02 wt% iodide ions.
- Sulfate, barium and / or iodide ions can be advantageously used to the
- the sulfate concentration can be adjusted so that the surface of the sensor is pH neutral
- the substance contains a proportion of 0.0004 to 0.02% by weight of magnesium ions. If the salt mixture contains magnesium, it can adhere particularly well to the carrier body
- the substance contains a proportion of 0.0004 to 0.008% by weight of nitrogen.
- Nitrogen combines with the ammonia and ammonium salts contained in human or animal skin and can be effectively used to neutralize it to keep the pH of the sensor surface neutral.
- the substance contains a proportion of 0.0001 to 0.006% by weight of phosphate ions.
- Phosphate ions themselves form a microporous layer in the microporous layer of the carrier body and thus achieves particularly good adhesion in the pores. Phosphate ions adhere very well to the surface of the carrier body. Due to the water-insoluble pores and the use of phosphate ions, the salts of the salt mixture are firmly anchored in the densest possible packing (crystal lattice). In addition, it is prevented that salt dissolved in moisture water is flushed out or dripped off.
- a further advantageous development of the invention provides that the sensors are connected in parallel, in series or as a combination of a serial circuit and a parallel circuit. Due to the different substances used a variety of different operating points of the same sensor can be set or the measuring range of the sensor can be set over a large range. In addition, it is possible to determine whether, for example during transport, certain humidity levels defined by the substances stored in the sensors have been exceeded, as a result of which a regularly set reversible change in the sensor behavior takes place in the sensors. Thus, after carrying out an operation, for example a transport, it is possible to ascertain, on the basis of the electrical properties of the circuit alone, whether certain operating points have been exceeded.
- a sensor arrangement comprising an air hose, which is provided over a partial region of its longitudinal extension with a sensor according to the invention, can be provided. It is further provided that a bypass line is provided, which is connected in an air-conducting manner with the air hose at two longitudinally spaced locations, wherein the bypass line has an opening for the admission of moisture to the sensor. With such a device, the humidity of flowing air or of flowing gases can be determined particularly quickly and easily.
- the senor has a coating, in particular containing or made of PTFE or porous silicone rubber, braided plastic, stainless steel mesh, porous ceramic, which is arranged between the bypass line and the sensor.
- the surface of the coating is larger than the surface of the sensor. This additionally extends the life of the sensor.
- a further preferred aspect of the invention provides a sensor device for determining the amount of liquid contained or stored in an object to be tested, wherein the sensor device comprises at least one heating element and at least one sensor according to the invention.
- the sensor device forms at least one lockable volume, in particular by contact with the surface of the object to be tested, wherein the heating element is designed to heat at least part of the volume limiting surface of the object, and wherein the humidity sensor Moisture inside the volume measures.
- a housing may be provided which has an end face in which a continuous opening is formed and in that the moisture sensor sealingly closes the opening from the side opposite the end face, wherein the volume is formed in, before or in the region of the opening ,
- This embodiment enables a particularly simple formation of a dense volume.
- Another aspect of the invention provides that the moisture sensor, in particular via a thermal adhesive, is in contact with the heating element. This improves the heat dissipation.
- the heating element is in contact with a thermally conductive body, in particular made of aluminum or aluminum sinter. This allows the formation of a thermally stable sensor device.
- the heating element is designed as a Peltier element and that between the housing, the body, the heating element and the humidity sensor is separated from the volume further volume is formed. This prevents a thermal short circuit of the Peltier element and improves the efficiency. In addition, the regulation of the temperature in the volume is simplified.
- the housing has a channel and / or that the body has a continuous recess, wherein between said continuous recess and the housing, a channel is formed.
- a further advantageous embodiment of the invention provides that the body, the heating element and the humidity sensor are pressed in the housing, wherein the housing is optionally bolted to the body.
- a volume created in this way is particularly dense. Air can not escape from the volume into the interior of the sensor device. In particular, moisture can not settle in the further air volume.
- a further preferred embodiment of the invention provides a device which comprises at least one sensor or a sensor arrangement on or in a holder made of a moisture-invariant, in particular non-magnetizable, and / or non-conductive material. This allows the formation of particularly robust sensors and additionally reduces the moisture-related material expansion of the sensor or the sensor arrangement ;
- a device for determining the moisture which has an opening to a material to be analyzed, in particular to the skin to be examined, after being placed on the material, in particular the skin, of a wall of a non-corrosive, moisture-invariant , preferably electrically non-conductive, non-magnetisable material, enclosed, having a defined volume analysis space, wherein at least in a portion of the wall at least one of said analysis room executed humidity sensor or a humidity sensor arrangement is arranged or at least a portion of the wall itself or is formed with such a sensor or such a sensor arrangement may be provided.
- This has the advantage that the humidity can be measured independently of the air movements of the ambient air.
- the air in the analysis room can be simply heated or cooled.
- a plurality of humidity sensors is arranged on the edge of the analysis space. In this way, a particularly accurate statement about the moisture distribution in the analysis room can be made.
- the invention provides a method of producing a method
- Carrier body and / or sensors for determining the moisture content of materials It is provided that the solution of moisture-water from a surrounding material or gas or air space reversibly and reproducibly receiving and / or to the material or the gas or air space donating substance, preferably such a salt on the inner and If appropriate, the outer surface of the carrier body is applied with or porous porous, non-hygroscopic, non-hygroscopic and high internal stiffness having carrier material, and the carrier body or acted upon with the solution of the substance carrier material to a predetermined temperature for at least partial evaporation the solvent is heated and solidifies the substance initially present in the pores of the carrier material, and optionally on the surface thereof and fixed there fixed and immovable.
- the solution of moisture-water from a surrounding material or gas or air space reversibly and reproducibly receiving and / or to the material or the gas or air space donating substance, preferably such a salt on the inner and
- the outer surface of the carrier body is applied with or porous porous, non-hy
- a salt layer on or in the pores of the carrier material can be produced in a particularly simple and accurate manner.
- a particularly good adhesion of the substance to the wall of the pores is possible by the special crystallization, which leads to a high mechanical strength.
- a detachment of the substance 3 from the carrier body 2 is thus only possible by thoroughly draining or rinsing the substance out of the carrier body, for example with water.
- a particularly advantageous development of the method according to the invention provides that during the application or after the application of the solution of the substance to the carrier body, the relative humidity of the air surrounding the carrier body is lowered and the salt is completely dried and / or during the application or after the application of the solution of the substance to the carrier body, the ambient temperature of the carrier body is set to at least 30 ° C.
- the ambient humidity of the process depends on the salt used as well as the salt mixture.
- the lowest possible ambient humidity proves to be particularly advantageous since drying is also possible for salts which are no longer in completely solid form from a certain ambient humidity. In the case of low ambient humidity, reversible air humidity characteristics are thus present.
- a printed circuit board material is used as the carrier material, in which by means of a laser, in particular bag-shaped, holes, pores or recesses are burned. This allows a particularly simple production of a sensor according to the invention on a printed circuit board and accelerates the manufacturing process, in particular in combination with an evaluation circuit.
- a particular aspect of the invention provides that the process of applying the solution and the subsequent drying process is repeated, in particular at least twice, repeated.
- the process of applying the solution and the subsequent drying process is repeated, in particular at least twice, repeated.
- the salt layer is applied to the carrier body by means of a spray coating process, wherein the salt dissolved in the solvent, in particular in a vacuum, is sprayed onto the carrier body, wherein in the area above the carrier body forms a mist of the solution, the settles on the rotated carrier body and forms a very thin salt layer.
- a spray coating process wherein the salt dissolved in the solvent, in particular in a vacuum, is sprayed onto the carrier body, wherein in the area above the carrier body forms a mist of the solution, the settles on the rotated carrier body and forms a very thin salt layer.
- a further particular aspect of the invention provides that a salt solution in liquid or gaseous form is sprayed or injected under high pressure into the carrier body for application of salt to the carrier body, optionally a positionable printhead for aligning the steam or liquid jet the carrier body is used. In this way, a particularly deep penetration of the salt in solution into the carrier body can be achieved.
- a further advantageous embodiment of the invention provides a simple and efficient method for disinfecting a sensor according to the invention, wherein the carrier body of the sensor is acted upon for a predetermined time with water vapor having a predetermined temperature of about 61, 5 ° C.
- FIG. 1 shows a possible embodiment of the invention with a base body 2 of Al 2 0 3 with a rough surface
- Fig. 2 shows an embodiment of the invention with fine-grained Al 2 0 3 as a support material of a carrier body and low surface roughness
- Fig. 3 shows an embodiment with platinum electrodes and average roughness at an electrode distance of about 10 ⁇
- Fig. 4 is an enlarged view of the salt layer on an electrode.
- FIGS. 5 and 6 show surface structures of the sensor with a smooth surface course.
- FIGS. 7 and 8 show a further embodiment of the invention with gold electrodes having a greater roughness and an electrode spacing of 16 ⁇ m.
- FIG. 9 shows the formation of superficial crystals at a very high concentration of the substance
- FIG. 10 shows a possible embodiment of a sensor circuit with a multiplicity of moisture sensors
- FIG. 1 schematically shows the arrangement of an RFID moisture sensor.
- FIG. 13 shows a further embodiment of a sensor according to the invention with a plurality of electrodes
- FIG. 14 shows an embodiment of an RFID sensor with an RFID antenna and a salt coating
- FIG 15 shows an embodiment of the invention analogous to FIG. 14 with deeper continuous pores, which are achieved, for example, by etching or burn-in by means of a laser
- FIG. 16 shows an embodiment of the invention with throughflow channels
- FIG. 17 shows an embodiment of the invention, the pores open on both sides and having a coating with the substance. With such a device humidity differences can be measured.
- FIG. 19 shows an embodiment of the invention with a heating resistor and a Peitierelement for achieving rapid response times of the sensor
- Fig. 20 shows an image of a porous base material in the pores of the Fig. 24 shows an embodiment of the invention in plan view with two electrodes and a plurality of pores arranged between these electrodes
- Fig. 25 shows a possible side view of the in Fig. Fig. 26 shows a further variant of the embodiment of the invention shown in Fig. 24 in a side view
- Fig. 27 a third variant of the embodiment of the invention shown in Fig. 24 in a side view.
- Fig. 28 shows an embodiment of a measuring circuit with a sensor according to the invention.
- FIG. 29 shows the measuring circuit of FIG.
- FIG. 32 shows a sensor for determining the skin moisture.
- FIG. 30 shows an npn transistor with a base layer, in the porous carrier body salt is introduced. Further advantageous embodiments of this development of the invention are shown in FIGS. 31a to 31f.
- FIG. 32 shows a device for detecting the air humidity above a surface emitting moisture.
- Fig. 33 shows another flexible embodiment of the invention on a plastic film.
- a further preferred embodiment of a sensor according to the invention is shown in FIG. 34 and serves to measure the air humidity in air ducts.
- FIG. 36 shows the cleaning and disinfection of a sensor according to the invention.
- a first embodiment of the invention is formed with a rough support body 2, which has a plurality of superficially formed bulges 201.
- the carrier body 2 consists of rough porous Al 2 0 3 .
- two bulges 201 are shown, of which the two outer bulges 201a and 201c are coated with a metal layer. This metal layer is vapor-deposited or sputtered onto the base body 2, for example, during production.
- the central bulge 201 b Due to the internal structure of the carrier body 2, the central bulge 201 b has a porous basic structure which is filled with a substance 3, in the present case sodium chloride in NaCl.
- the salt layer to the carrier body 2 by means of a spray coating method.
- the salt dissolved in a solvent in particular in a vacuum, is sprayed onto the carrier body 2, wherein a mist of the solution forms in the region above the carrier body 2, which precipitates on the rotated carrier body 2 and forms a very thin salt layer 32 ,
- Another possibility for applying salt to the carrier body is to spray or inject a salt solution in liquid or gaseous form under high pressure into the carrier body 2.
- a positionable printhead can be used to align the vapor or liquid jet with the carrier body 2. The solution arrives very well in pores of deeper layers of the carrier body 2.
- the base body 2 As shown in Fig. 1, the base body 2, a number of multi-pore connecting channels 31 which are filled with this substance. Also, the metal layer that covers the two outer bulges 201 a, 201 c, has a number of pores or micro-recesses 33, which are filled with the substance 3. On the one hand, the metal itself may be porous. On the other hand, many metals have a rough surface, which is sufficient to have enough micro-bumps or small holes where the salt can anchor.
- the entire sensor arrangement comprising the main body 2, the metal coatings on the two outer bulges 201 a, 201 c and the middle, filled with salt bulge 201 b is coated with a salt layer 32 or covered.
- the salt layer which consists of sodium chloride NaCl, is in communication with the salt-filled channels 31 and the salt components contained in the recesses 33.
- the two metal layers form electrodes on which an alternating voltage can be applied, whereby a current flow or a charge shift between the two electrodes 4 can be measured. It is particularly advantageous for the outer contacting that the salt layer at the point of contact with the outer feed line does not completely cover the electrodes 4, so that a direct contacting of the feed line with the metal layer is possible.
- the salt introduction is usually the last production step. Subsequent steps to apply insulation are possible if the insulation is permeable to water vapor.
- platinum is used in this embodiment of the invention.
- Fig. 2 shows a further embodiment of the invention, wherein the base body 2 has a finer surface structure.
- a finer high- or dead-burnt alumina Al 2 0 3 is used, which has a smaller pore size, than the aluminum oxide used in FIG.
- the gold layer 33, which forms the electrodes 4, has superficially porous recesses 33.
- salt 3 ' is present in channels 31 of the porous carrier material of the carrier body 2.
- the gold electrodes need not be porous.
- the normal surface roughness for anchoring the salt layer on the electrodes is sufficient since microholes and unevenness in the production process of the electrodes occur naturally and are distributed statistically.
- These salt channels extend to the surface of the carrier body 2, on which the two electrodes 4 are arranged, namely vapor-deposited or sputtered.
- the sensor 1 is completely coated with a layer of sodium chloride in this embodiment as well.
- This layer of sodium chloride is in communication with the sodium chloride in the channels 31 and also fills the recesses 33 in the metal layers of the electrodes 4.
- a contacting of the electrodes 4 takes place analogously to the embodiment of FIG. 1.
- the support body 2 has a rough surface as shown in FIG. 1 or a smooth surface as shown in FIG.
- metal layers are vapor-deposited or sputtered onto the carrier body 2, these metal layers subsequently being used as electrodes 4 for contacting with external components.
- the electrodes 4 typically have a layer thickness of 0.5 ⁇ m.
- a solution is dropped into the intermediate region 220 of the carrier body 2 between the two electrodes 4 or onto the bulge 201 b between the two electrodes 4 by means of a pipette.
- This solution advantageously contains water as solvent and sodium chloride as dissolved salt.
- the salt passes into the channels 31 and fills them up.
- the carrier body 2 is heated to a temperature of, for example, 40 ° C., whereby the water volatilizes out of the pores 32 and the salt 3 combines with the porous carrier material of the carrier body 2 or crystallizes out on its surface.
- the salt 3 Due to the superficial wetting of the porous carrier body 2, the salt 3 reaches very far into the carrier body 2 and in particular is distributed homogeneously therein. After evaporation or evaporation of the solvent, the salt 3 in crystal form is firmly bonded to the carrier material of the carrier body 2.
- FIG. 20 shows an alumina structure that can be used to form a carrier body 2.
- the two areas designated by the reference symbols 41, 41 ' are images of the electrodes covered by the salt layer
- the two remaining areas 42, 42' show the intermediate areas covered by the salt layer 32 with the pores 31 filled by the salt layer.
- 4 shows the surface structure of the salt layer in the area above the electrode 4.
- the two electrodes have a spacing of 10 pm and a thickness of likewise about 10 pm. Particularly evident is the formation of relatively large homogeneous salt crystals in the region above the electrodes 4 and a rather rugged surface structure in the region between the electrodes.
- FIG. 5 shows a picture of the surface structure between the two electrodes with a low salt concentration.
- the relatively smooth surface course and the small number of superficial salt crystals 421 are striking.
- a low drying temperature provides sufficient time to achieve a homogeneous distribution during crystallization.
- Fig. 6 shows a surface comparable to the surface shown in Fig. 5, but with a higher salt concentration.
- FIG. 7 shows a rougher surface structure similar to that shown in FIG.
- the electrodes as well as the intermediate region of the electrodes are fabricated at intervals of 15 ⁇ m.
- FIG 8 shows two electrodes 41 covered by a salt layer and an intermediate region 42 in which the carrier body 2 is directly covered with salt.
- Fig. 9 shows one prepared with an extremely large salt concentration
- the sensor 100 is connected with its two electrodes 4 to an AC voltage source 17, which is a voltage to the two electrodes of about 25m, typically from 100mV to 1V.
- the impressed AC voltage has, for example, a frequency of 35 kHz to 5 MHz.
- a current measuring device 16 can be connected in series with the sensor 1. Such a measuring circuit is shown in FIG. 28.
- the frequency used for the measurement should be approximately in the range of 50 kHz to 5 MHz.
- the conductance can be measured by a variety of methods, such as the IV method, the RF-IV method or the auto-balancing method.
- Another application of a sensor according to the invention is to detect an increase in the humidity over a certain relative humidity.
- the effect is exploited that every salt undergoes an irreparable change in the coating at a certain relative humidity by a single state of aggregate state change from solid to liquid.
- the salt or parts of the salt drips or drips off as drops, if necessary, the uniformity of the salt coating can also change, as a result of which permanent changes in capacitance value or conductance changes occur.
- it can be determined directly and unambiguously by means of a sensor according to the invention whether an increase in humidity over a threshold value has been achieved.
- the following table describes the relative humidity values for a variety of salts:
- the humidity threshold of the salts is changed.
- Each of the salts mentioned is irreversibly changed by a different relative humidity on the sensor.
- ammonium nitrate and magnesium nitrate may be used instead of the salt shown in Figs.
- the manufacturing process of such a sensor is modified to form the solution with the same mass proportions of sodium chloride and potassium chloride.
- the thresholds Iwert-humidity which is required to destroy a sensor according to the invention, behaves in mixtures of salts or substances 3 approximately according to the weighted with the mass parts of the respective substances mean threshold air humidities, which destroy a sensor with the two pure substances to lead.
- FIGS. 10 and 12. 12 shows the parallel connection of a multiplicity of humidity sensors 1a, 1b, 1c, 1n. Each of these sensors has a different threshold air humidity, above which an irreversible destruction of the respective sensor takes place. After completion of the production there is a parallel connection of the sensors, each of the sensors being intact. With a given temperature and humidity, a capacity or a conductivity can thus be determined. Each of the individual sensors has a different threshold air humidity.
- the humidity sensors whose threshold humidities are graded at intervals of 10% each, are connected in parallel arranged. Achieved, as shown in Fig. 12a, the relative humidity exceeds 20, but below 30%, the sensor 1d irreversibly destroyed, the sensor 1 c with a threshold humidity of 30%, however, remains intact. If the relative humidity is increased to 44% relative humidity, the sensors 1 b, 1 c and 1 d are irreversibly destroyed, while the sensor 1 h remains intact.
- such a sensor arrangement can be transported together with a cargo, wherein the maximum allowable humidity for the cargo is 30%.
- each of the sensors 1a, 1b, 1c, 1d is completely intact.
- An increase in humidity to 27% during transport destroys sensor 1d.
- the sensor can be connected to an evaluation unit, whereby the irreversible destruction of the individual sensors can thus be determined. If a sensor is irreversibly destroyed, its conductance and its capacity are significantly reduced. As a result, the conductance or the capacitance of the overall arrangement is also reduced, which can be measured by means of an evaluation unit, in particular with the evaluation unit shown in FIG. 29. If the maximum air humidity during the entire transport 27%, as shown in Fig. 12a, it can be assumed that the cargo is intact.
- FIG. 13 Another embodiment of the invention, shown in FIG. 13, comprises a plurality of electrodes made of a porous material or of a material having recesses on the surface. These recesses are, as well as the pores of the carrier body 2, filled with a salt 3. In this case, an additional increase in the capacitance or the conductance can be achieved via the inclusion or incorporation of salt crystals in the electrodes.
- FIGS. This is a base body 2, which has a recess 201.
- the support material of the carrier body 2 is, as described in the previous examples, porous, wherein the salt used to increase the capacitance or conductance is contained both in the pores 31 of the base body 2 and in a base body 2 covering layer.
- the layer or the pores 31, 32 are arranged in the region of the recess 201 of the carrier body 2.
- the recess is In this case, the recess 201 defines an analysis space 83 when the base body 2 is placed on an illustrated fabric layer 7.
- the salt layer 32 is in contact with the gas located in the interior of the analysis space 83, preferably air.
- two electrodes 4 are introduced, which completely pass through the carrier body 2.
- the support body 2 is completely interspersed in the region between the two electrodes 4 with channels 31 with salt coating.
- the carrier body 2 has an opening 81 which forms an analysis space 83 when placed on a moisture-emitting body.
- This opening 20 has, in particular the shape of a trough.
- the size of this tub determines the analysis space 83, whereby quite different tub sizes and tub shapes are possible.
- the height of the tub, thus the distance of the salt layer 32 to be measured object 121 is about 1-5 mm.
- Another feature of the embodiment of the sensor is an RFID antenna, in Figs. 14 and 15, which is arranged on the back of the base body 2 and under the salt layer 32 and the opening 81 in which the salt layer 32 is embedded, and is arranged on the side opposite the trough of the support body 2.
- the essential difference between the embodiment shown in FIGS. 14 and 15 is that, due to the different width, size and shape of the pores, a different dependence behavior of capacity and conductance with respect to the air humidity can be established.
- a device for measuring the conductance or the capacitance directly onto the carrier body 2.
- a current measuring device or a voltage source are formed on the substrate in contact with the carrier material of the carrier body 2.
- a sensor comprises an RFID communication unit which transmits the determined humidity data by means of RFID communication to a communication controller.
- a modified variant can be applied, the realization of which is much easier.
- a capacitor is connected in parallel to the RFID antenna, which stores the radiation energy received by the RFID antenna at short notice.
- Such a capacitor has about a capacity of about 100 nF to a few pF.
- a particular embodiment of the invention now provides that instead of a conventional capacitor, the intermediate region between the two electrodes, which is parallel to the antenna, acts capacitively and stores the power consumed by the antenna at short notice.
- the capacity of the condenser varies, increasing the available energy with increasing humidity. If the humidity value of the sensor 100 is interrogated by an external RFID unit, this transfers electrical energy to the sensor 100, wherein only an energy amount predetermined by the condenser and thus by the air humidity can be stored in the sensor 100.
- the sensor comprises a transmitting unit which continuously extracts energy from the capacitor formed by the humidity sensor between the two electrodes 4 and emits a pulsed signal.
- a further embodiment of the invention shown in Fig. 16, provides that the material of the base body 2 is only superficially filled with salt 3 and has a salt layer.
- the remaining, open pores form flow channels, whereby ambient air can flow through the pores of the substrate. Moisture contained in the air condenses much faster in the salt. The prevailing moisture in the salt is also dried or absorbed much faster by the air flow.
- FIGS. 25, 26 and 27 Different configurations of a sensor according to the invention in plan view and in side view are shown in FIGS.
- the electrodes 4 are formed by metal cuboids, between which the porous material of the main body 2 is located.
- the embodiments of FIGS. 25, 26 and 27 basically have the same plan view; as shown in Fig. 24, on.
- the carrier material of the carrier body 2 is located both in the region below the electrodes 4 and also in the region directly between the electrodes.
- Salt is introduced substantially into the pores 21 1 in the carrier material of the carrier body 2 between the electrodes 4. Only individual pores in the area below the two electrodes are filled with salt.
- a further embodiment of the invention, shown in Fig. 26, shows the two electrodes 4, which are placed on a support body, that is vapor-deposited or sputtered. In the immediate intermediate region between the two electrodes is a superficially adhering to the carrier body, located outside the pores salt layer. In the area below this salt layer, the pores are filled with the salt 3.
- FIG. 27 shows a sensor 100 with two electrodes 4, which are applied to a base body 2.
- the ambient air can flow directly to the main body 2.
- the pores in the intermediate region between the two electrodes 4 are filled with salt 3.
- FIGS. 21, 22 and 23 show different embodiments of a salt layer on the surface of the carrier material of the carrier body 2.
- a salt layer on the surface of the carrier material of the carrier body 2.
- lower salt concentrations and smooth surface courses of the support body 2 allow crystalline salt structures to crystallize.
- the manufacture of a sensor 100 there is basically a trade-off between a fast response and a good reproducibility of the sensor.
- FIG. 21 shows a particularly smooth surface course and a salt layer with a particularly low salt concentration.
- the salt crystals are extremely homogeneous and are relatively clearly separated from each other.
- Such a sensor 100 provides a rather slow response due to the small surface facing the ambient air, but overall, sensors thus produced can be manufactured with great geometrical precision.
- Fig. 23 shows a sensor with an extremely rough surface, which allows a particularly fast response. Disadvantage of this sensor is that a plurality of identically manufactured sensors have large geometric differences and sometimes have very different characteristics.
- FIG. 22 shows a tradeoff between the two extremes shown in FIGS. 21 and 23.
- This structure has a relatively good response time of about 5 seconds, whereby the reproducibility of the results is ensured by a post-manufacturing calibration of the sensors.
- FIGS. 17 a, 17 b and 18 A further particular embodiment of the invention is shown in FIGS. 17 a, 17 b and 18.
- the trough-shaped openings 212, 213 are provided in the carrier body 2, which are opposite to each other on the carrier body 2.
- the porous subregion is filled with salt 3 'in each case up to a predetermined depth.
- both trays have a salt layer 23 in their bottom area.
- a plurality of comb-shaped electrodes 4 is provided between the carrier body 2 and the salt layer 23, a plurality of comb-shaped electrodes 4 is provided. In this case, the comb-shaped arrangement of the electrodes is shown in FIG.
- each sensor shown in Fig. 17a has in each case four ports, namely two ports 47 for each of the two sides.
- comb-shaped electrodes 4 In the lower region of the trough-shaped recess between the carrier body 2 and the salt layer 32 are two comb-shaped electrodes 4, whose terminals 47 are each connected to the RIFD antenna.
- the comb shape of this sensor is shown in Fig. 14b.
- the end face 29 abutting the trough-shaped recess 83 on the material 7 to be measured can be provided with a surface which enables an improved adhesion of the sensor to the material to be measured.
- This can be done for example by a nanostructured surface, which are designed, for example, as cantilevers, which adhere to any surface. Only lateral shear forces make it easier to remove such a fitted sensor. All adhesives accessible to a person skilled in the art, which do not evaporate after drying and which can not influence the signal of the humidity sensor, are likewise used.
- Flow channels are formed by open, not filled with salt pores of the substrate. It is advantageous that the pores of the material can be flowed through well and the flow through the pore size of the material in the preparation of the carrier body 2 can be set in advance. Moisture contained in the air can thus be rapidly transported through the base body 2 to condense on the salt or in the salt-filled pores. Furthermore, the through-flow of dry air, that in the salt-filled pores water can be removed quickly.
- the flow velocity for example of the ambient air, can be measured by comparing the measurement result of a sensor through which air flows with that of a sensor which has not flowed through. Dodge the values of the perfused and not flowed through sensor strongly from each other, it can be assumed that the flow velocity in the region of the sensor is very large.
- FIG. 1 An embodiment of a differential or differential flow rate meter with flow channels is shown in FIG.
- the flow channels are located between the salt-filled pores of the upper and the lower trough of the sensor shown in Fig. 18.
- the communication between the RFID reader and the RFID tag is shown schematically in FIG. 11.
- the information is transmitted by means of near-field communication from an RFID tag to an RFID reading device, which evaluates the transmitted data and makes it available for further processing, for example to a computer or a computer system.
- FIG. 1 Another particular embodiment of the invention is shown in FIG.
- the pores of the carrier material are filled with a metal, in particular gold or platinum.
- a metal in particular gold or platinum.
- circuit board material which is roughened on the surface or into which channels are etched or baked by means of a laser or an etching process can be used as the carrier material for this purpose.
- the resulting pores are filled with metal or metal is vapor-deposited or sputtered onto these pores.
- a similar procedure can also be used with other carrier materials, for example aluminum oxide or titanium oxide.
- one electrode or both electrodes may be formed with salt. Since electrodes 4 formed from salt themselves have a conductivity of 100 kOhm up to 100 ohms, the salt can also be used as electrode material.
- a further particular embodiment of the invention shown in FIG. 31, provides an air humidity sensor 100 arranged on a printed circuit board, an electrode 4 being arranged on each of the two sides of the printed circuit board.
- the two electrodes are directly opposite each other on the printed circuit board 23, wherein in the region between the two electrodes 4 a continuous recess 24 is provided, which is covered with a salt layer 32.
- the two electrodes 4 may be surrounded by the salt layer 32.
- the two electrodes 4 are in contact with the salt layer, wherein they partially cover the surface 24 covered with the salt layer recess 24.
- the production of the electrodes can be carried out in such a way that a number of channels 44 are introduced into the laser by means of a laser or by means of an etching process Printed circuit board material is baked or etched and then the electrode material is applied in the channels and superficially on the carrier body.
- a hole 24 is drilled or milled into the circuit board by a conventional drilling method.
- channels 44 can be introduced into the region below the electrode 4 to be provided by means of a laser or an etching process.
- salt 3 is introduced into the recess 24 in aqueous solution, this salt remaining in the recess due to the capillary effect. After the evaporation of the solvent, which can take place particularly rapidly, especially at elevated temperature or reduced atmospheric humidity, the dropping of a further drop of the solution with the selected substance, in particular sodium chloride or potassium chloride, can take place. After repeated dripping, a salt layer 33 forms in the inner region of the recess 24.
- the metallic electrodes 4 can be vapor-deposited or sputtered on, wherein the metal preferably also solidifies in the previously formed channels. After complete fabrication of the electrodes, they may optionally be coated with salt by re-dripping the salt solution.
- FIGS. 31a to 31d Further advantageous embodiments of this development of the invention are shown in FIGS. 31a to 31d.
- Fig. 31a shows an arrangement analogous to Fig. 31 e, in which the two electrodes 4 are not opposite each other, but have a maximum distance from each other.
- Figs. 31b and 31c show the embodiment of Fig. 31a from above and from below, respectively.
- Fig. 31d Another embodiment of the invention is shown in Fig. 31d.
- the two electrodes are located on the same side of the printed circuit board 32. It is advantageous that the production is easier and one-sided layouts can be used for the circuit design.
- Fig. 31f shows the arrangement of Fig. 31d from above.
- the electrodes are not coated with salt.
- Another embodiment in which the electrodes are coated with salt is also possible, but not shown.
- FIG. 28 is a semiconductor device produced by modifying a bipolar transistor, in this case an NPN transistor.
- the base layer is through a filled with carrier material and acted upon with salt base layer replaced.
- continuous channels are preferably burned into the carrier material by means of a laser and salt is fed into the channels.
- a base electrode which can be used to change the operating point of the transistor arrangement.
- the increase in the conductance in the base region between the two end-doped layers leads to a current plus between the collector C and the emitter E without application of a base bias.
- a base bias is applied, the current flow between the emitter and the collector can either be boosted or inhibited ,
- different characteristics of a sensor can be provided depending on the humidity.
- Figs. 30a and 33b Another embodiment of the invention is shown in Figs. 30a and 33b, respectively.
- 150 carrier material 2 is applied to a thin plastic film.
- the layer thicknesses of the plastic film or the rotary body amount to about 50 to 500 pm.
- a metal layer 400 is applied on the carrier layer 2.
- one or more electrodes 4 are etched out of the carrier body 2 by means of etching medium penetrating into the metal layer 400.
- This embodiment can be applied in general terms for each control electrode of field-effect transistors, where a salt layer or salt in the pores permits a humidity-dependent control of the transistor.
- a salt layer or salt in the pores permits a humidity-dependent control of the transistor.
- the control electrode is a JFET, MESFET, MOSFET, MODFET, Tyristor od.
- the salt coating can also be incorporated into any pn diode, Schottky contact, MOS capacitor, zener diode, varactor, pin diodes, tunnel diodes, Schottky diodes as an additional humidity-dependent coating that makes the operating point humidity dependent.
- Common to all versions is the integration of the salt separately connected in front of the control electrode or connection or integrated in the control electrode or connection.
- humidity-dependent resistors at any other connection can include drain, source, emitter, collector or the like. Stand alone or together with the control reflection, which also contains a salt stratification.
- FIG. 34 A further preferred embodiment of a sensor for determining the humidity is shown in FIG. 34.
- the carrier body 2 of the moisture sensor is made of aluminum oxide Al 2 0 3 and has an open-pore porous structure.
- the embodiment with aluminum oxide Al 2 0 3 represents only one possible embodiment of the invention, quite generally any open-pore porous, humid-invariant, non-hygroscopic and high internal stiffness having support materials can be used.
- substances 3 which are present in the form of salt mixtures or mixed crystals 3.
- a solution is created that evaporates its aqueous portion and deposits crystalline salt on the carrier.
- the dissolved in the solution components as well as the salt-embedded portions of the substances shown below are each referred to as ions.
- the salt mixture contains the following ions in% by weight:
- Na and Cl ions generally serve as ion conductors. Their conductivity and specific permittivity depend on the amount of water absorbed. The more water dissolved in the salt mixture, the greater the detected permittivity. Na and Cl in this case has a conductivity and permittivity which clearly corresponds over several orders of magnitude to the amount of water stored in the salt. In particular, Na and Cl have very little saturation effects. The differential change in conductivity at increasing or decreasing humidity or anaerions aer in üaiz stored amount of water is constant over several orders of magnitude.
- Potassium ions are added to the salt mixture to allow faster and stronger sensor response at particularly low humidities. If small concentrations of less than 0.05% by weight of potassium ions are added to the salt mixture, then it can be achieved that, at very low humidities, a greater response of the conductivity to stored water or to atmospheric moisture takes place. Potassium has a specific electrical conductivity of 14.3x10 6 A / ( v " m ) Thus, even areas of very low humidity, which are only very roughly dissolved by NaCl, can be better represented: too much potassium, more 0.2% by weight may cause the sensor as a whole to become too conductive and saturation effects to result, resulting in reduced sensor accuracy in the range of higher humidities.
- Potassium may be present in the salt mixture in the range of 0.005 to 0.02% by weight.
- iron ions in particular iron (III) ions and magnesium ions.
- carbonate ions are additionally present in the salt mixture, there is the additional advantage that they are practically insoluble in water after adhering to the support body 2 and serve as a stabilizer of the NaCl. Carbonate is used as a desiccant to deliver water so that a carbonate-containing sensor can be used more quickly.
- Carbonate especially calcium carbonate
- Carbonate is used to dry solvents, especially when the boiling point of the solvent is above the melting point of potassium but below the melting point of sodium. Then the potassium is molten in the boiling solvent and its surface does not encrust. It thus requires significantly less alkali metal and it can be almost completely consumed in the drying process, so that only very small residues must be disposed of.
- Carbonate ions can be present in the salt mixture in the range from 0.005 to 0.02% by weight. Bromide ions form, in particular together with one of the metals iron, potassium, magnesium, salts, which, once the liquid-dissolved phase is dried, have the following advantageous properties.
- the resulting mixed salt is improved water soluble, which increases the absorption of water.
- potassium bromide has a solubility in water of 650 g / l over NaCl (359 g / l), measured at 20 ° C.
- bromide ions in the salt mixture provides for a faster response of the sensor. Bromide ions are not washed out of the pores of the support material 2 even if 100% relative humidity is present. There is no leaching by 100% moisture instead.
- bromide ions are superficially present in the form of iron (III) bromide, this results in a faster transport of cations and anions, especially of the Na and Cl ions, by sublimation. There is a space exchange of the ions in the lattice and thus an acceleration of the response. When heating above 200 ° C, a complete reorganization of the salt structure takes place.
- Bromide ions can be present in the salt mixture in the range between 0.002% by weight and 0.08% by mass.
- Potassium bromide and magnesium bromide are used to accelerate the response of the sensor as the conductivity of water is much greater than that of NaCI.
- a concentration of more than 0.2% by weight or the sole use of potassium bromide or magnesium bromide instead of NaCl causes the salts to be flushed out of the carrier body.
- a bromide salt contains bromide ions (Br-) in its ion lattice, which are simply negatively charged.
- the inorganic bromides include, for example, the salts iron (III) bromide (FeBr3), potassium bromide (KBr), lithium bromide (LiBr) magnesium bromide (MgBr2), sodium bromide (NaBr), rubidium bromide and silver bromide (AgBr).
- Iron (III) bromide decomposes at temperatures> 200 ° C to form iron (II) bromide and bromine. The reaction is reversible at lower temperature.
- Potassium bromide is the potassium salt of hydrogen bromide, which forms colorless crystal cubes, which are even better soluble in water than potassium chloride, with a solubility of 650 g / l at 20 ° C.
- the solubility of magnesium bromide in water is 1015 g / l at 20 ° C.
- Calcium ions can be added to the salt mixture and serve as
- Desiccant ensure the stability and strength of the salt crystal in the pores.
- Calcium ions are preferably added to the salt mixture in the form of calcium carbonate.
- flooding can be prevented because carbonate is almost insoluble in water once it adheres to the surface of the pores of the support member.
- Calcium ions can be present in the salt mixture in the range between 0.001% by weight and 0.06% by mass.
- Sulfate ions can be advantageously used to minimize the effects of contamination of the sensor surface as possible.
- the sulfate concentration can be adjusted so that the surface of the sensor is pH neutral. If the surface is contaminated, for example by contact with the object to be measured, the provision of a pH which corresponds to the pH of the object to be measured prevents superficial reactions from taking place.
- the impurities do not react with the surface of the sensor and can easily be removed from the surface by heating and evaporation.
- Sulphate ions can be present in the salt mixture in the range between 0.0007% by weight and 0.02% by mass. Barium and iodide ions are simply negative binding partners for reactive
- Barium and iodide ions serve to neutralize the pH of the sensor surface and have the same effect as sulphate ions.
- Barium ions can be present in the salt mixture in the range between 0.0004% by weight and 0.04% by mass.
- Iodide ions can be present in the salt mixture in the range between 0.0004% by weight and 0.01% by mass.
- the salt mixture contains magnesium, then this can adhere particularly well to the carrier body 2.
- a porous coating or a porous coating of the pore inner walls of the carrier body 2 is formed which adheres well to the carrier body 2 on the one hand and well to the other salts of the salt mixture on the other hand .
- Magnesium once it has adhered to the surface of the porous support material, is insoluble in water and provides one resistant to reactions with hydrogen fluoride and alkalis.
- Magnesiumsuitat can optionally be added as an additional drying agent.
- Magnesium compounds are added to the solution in ultra-fine powder form. In addition, it is prevented that salt dissolved in moisture water is flushed out or dripped off.
- Magnesium ions can be present in the salt mixture in the range between 0.0004% by weight and 0.02% by mass.
- Phosphate ions themselves form a microporous layer in the microporous layer of the carrier body 2 and thus achieves particularly good adhesion in the pores. Phosphate ions adhere very well to the surface of the carrier body 2. The water-insoluble pores and the use of phosphate ions, the salts of the salt mixture in the densest possible packing (crystal lattice) are firmly anchored. In addition, it is prevented that salt dissolved in moisture water is flushed out or dripped off.
- Phosphate ions can be present in the salt mixture in the range between 0.0001% by weight and 0.006% by mass.
- Nitrogen can also be advantageously contained in the salt mixture. It combines with the ammonia and ammonium salts contained in human or animal skin and can be effectively used to neutralize it to keep the pH of the sensor surface neutral.
- Nitrogen can be present in the salt mixture in the range between 0.0004% by weight and 0.008% by mass.
- the respective salt may also contain nitrogen, which is incorporated into the salt lattice in this without solid bond.
- the salt When producing a salt in the atmospheric environment or in the usual atmosphere, the salt contains nitrogen embedded in the range of 0.0005 to 0.005 wt%, in particular of about 0.001 wt%. The longer the drop is exposed to the nitrogen-containing atmosphere during the manufacture and drying of the sensor, the higher the nitrogen content in the salt mixture.
- the content of nitrogen in the salt mixture can be increased by preparation in a pure nitrogen atmosphere. The incorporation of nitrogen into the salt mixture can be prevented by preparation in helium atmosphere.
- the salt mixture contains impurities up to a maximum of 0.0005% by weight.
- the impurities contain in particular lead and other heavy metals.
- Hexacyanoferrate can be added to the salt mixture to improve the flowability up to a concentration of 0.0001% by weight.
- the neutralization of the pH decouples the dependence of the measurement result on the presence of special substances in the environment.
- Properties of the environment - except for the humidity to be determined - thus have no influence on the measured value of the sensor.
- human skin in addition to water vapor, fumes many other gases and liquids, and adhering these to the surface of the sensor would increase its conductivity.
- iron, magnesium or sulfate ions the surface is pH-neutralized. Dirt does not react with the sensor and can be removed from the sensor by heating or drying the sensor.
- a given crystal lattice in the pores is created with the specified ions, which has a substantially octahedral spatial structure.
- the other ions and atoms present in the solution can also be easily incorporated into the salt mixture.
- the salt mixture is dissolved in one liter of pure water.
- a preferred salt mixture is prepared, which is composed by means of the following salts:
- any other combinations of salts with the ions shown can be used as starting materials.
- the specified salt mixture does not necessarily have to be used. It is also possible to use other starting materials which are mixed into a solution having the same ion concentration.
- the aqueous solution of the salt mixture has about room temperature, in particular 20 ° C. Alternatively, a slightly higher temperature may be used to achieve better solubility. The temperature is less than 30 ° C. In the present embodiment, a solution containing about 1 mg of the salt mixture per 1 ml of water is used. There are about 1g / l salt dissolved in the water. Mixtures can be used from about 0.1 g / l up to 6 g / l.
- the solution is dropped onto the carrier body 2.
- the carrier body used is Al 2 O 3, which has a pore size of about 500 nm.
- the moisture-sensitive surface of the sensor is 5 mm ⁇ 5 mm.
- the carrier body 2 is heated to a temperature of 65 ° C. Drops can be dripped in different sizes and can be dispensed with appropriate drippers in drop sizes of about 25 nanoliters. Typical droplet sizes for the production of homogeneous surfaces of sensors with a few mm 2 surface are 10 ⁇ to 1 15 ⁇ .
- the drop of the solution is dropped before the carrier body 2 is heated.
- the heating of the carrier body 2 takes place after dripping.
- the carrier body 2 is cooled again after the solution water has completely evaporated.
- the thinning takes about 10 to 15 minutes.
- This process is repeated a few times, until finally the desired incorporation of salt 3 'is carried out in the carrier body 2.
- the support body 2 is withdrawn at each repetition of the process, since otherwise seed crystals can appear, on which the salt preferably settles.
- the dimensions of the seed crystals are larger than the diameter of the pores.
- the individual constituents of the salt mixture 3 ' are dissolved in the water, in other words, decomposed by the liquid phase.
- the dissolved substance mixture is applied to the carrier body or to the pore substrate.
- a stepwise defined incorporation of the substances takes place. Due to the mass (weight) and the reactants present, stable compounds are created which give an exact non-aging coating within the pores.
- the crystal lattice constants of the elements and the pore diameters, as well as the amounts of substance, result in defined sensor properties. Depending on the concentration, a particularly rapid response or a particular stability can be achieved.
- a protective coating that does not allow molecules larger than water vapor to pass through provides special protection in sensitive environments (skin measurements).
- the design as a disposable hygiene cap provides a special protection for patients from the transmission of disease by the sensor.
- the water of the solution evaporates when the carrier body 2 and the solution itself has a temperature between 35 ° C and 75 ° C in order to prevent clumping of the salt on the surface of the carrier body 2.
- very small drops of a few nanoliters are applied to the surface of a printed circuit board acting as carrier body 2 or to the surface of a semiconductor.
- FIG. 34 A further preferred embodiment is shown in FIG. 34 and serves for measuring the air humidity in air ducts, in particular compressed air ducts.
- This exemplary embodiment of the invention shows an air hose 250 which is provided with a sensor element 251 over a partial region of its longitudinal extent.
- the sensor element 251 has a housing 252 surrounding the air hose.
- a bypass line 253 is provided, which is connected to the air hose 250 at two longitudinally spaced locations 254, 255 in an air-conducting manner. If air is passed through the air hose 250, a part of the air guided into the air hose 250 also passes through the bypass line 253.
- the bypass line 253 has an opening 256 through which moisture can reach a sensor 257.
- the sensor 257 has a construction according to the invention. Further, to reduce the contamination of the sensor 257 by the passing air, a Coating 259 is provided, which is arranged between the bypass line 253 and the sensor 257.
- the coating 259 may be porous films, e.g. As PTFE or porous silicone rubber, braided plastic, stainless steel mesh, contain porous ceramic or consist of these materials.
- the sensor 257 and the coating 259 are enclosed in a cover plate 260 which is fixedly connected to the housing 252 and fixes the relative position of the sensor 257, the coating, the bypass line 253 and the air tube 250.
- the surface of the coating is larger than the surface of the sensor 257. This increases the life of the entire assembly if the air to be measured is heavily soiled, such as when oil and other particles clog the coating. By choosing a larger surface of the coating, the time to complete blockage is also increased.
- FIG. 35 shows a specially designed measuring head 70 with a housing 75, which has an opening 79 on its end face 78.
- the housing 75 is made of plastic.
- ABS Teluran or other plastic can be used, which has a low water absorption capacity.
- the volume 71 has the thickness which corresponds to the thickness of the housing 75 in the region of the opening 79, in the present embodiment, the thickness is about 1 mm.
- the area of the opening in this embodiment is about 4 mm 2 .
- the volume 71 is open from the end face 78, so that ambient air can penetrate into the volume 71.
- the volume is closed airtight by the humidity sensor 73 from the opposite side.
- the humidity sensor 73 is constructed as a moisture-sensitive, resistive and capacitive element. In this specific embodiment, it is a salt-containing humidity sensor 73, as described above.
- the terminals 83 of the humidity sensor 73 which are used for the electrical measurement of humidity, are outside the volume.
- a heating element 72 is arranged on the side facing away from the volume 71 of the humidity sensor 71.
- a Peltier element was chosen for this, but it is also possible to choose any other heating element 72.
- the heating element 72 lies with its two thermally active surfaces on the entire surface of the humidity sensor 73. Thus, it is possible to either heat the humidity sensor 73 or - if necessary - to cool.
- the heating element 72 has two electrical connections 82, by means of which the heating element 72, depending on the polarity, can supply heat to the humidity sensor 73 or dissipate heat from the humidity sensor 73.
- the heating element 72 is adhesively bonded to the humidity sensor 73 in this specific embodiment.
- the illustrated embodiment has a thermally conductive body 74, which consists in the present example of aluminum with a thermal conductivity of 236 W / (m K). In general, other heat conducting materials such as metals may be used for this body 74, but aluminum and sintered aluminum are particularly suitable.
- the body 74 is located on the moisture sensor 73 flat. The body is connected in this preferred embodiment with the humidity sensor 73 via a thermal adhesive.
- the body 74 has a channel 76 for receiving the terminals 83 of the humidity sensor 73 and the heating element 72.
- the diameter of the channel 76 is chosen so that the terminals 83 of the humidity sensor 73 and the heating element 72 can be easily passed.
- the channel 76 leads from the region of the heating element 72 and the humidity sensor 73 adjacent thereto through the body 74 to a control unit (not shown) located at the other end of the body 76.
- the channel 76 is formed by a recess or notch in the body 74 and an adjoining part of the housing 75.
- the thermal conductivity of the heating element 72 and the humidity sensor 73 is in the range of 28 W / (m K) and corresponds approximately to the thermal conductivity of aluminum oxide (99.6% CC-AI203).
- Water vapor has a thermal conductivity of 0.0248 W / (m K).
- Air (21% oxygen, 78% nitrogen) has a thermal conductivity of 0.0262 W / (m K).
- precipitating water has a much higher thermal conductivity of 0.5562 W / (m K).
- the side of the heating element 73 and the humidity sensor 73 is a circumferential volume 71 densely separated from the volume, further filled with air volume 77, which leads into the channel 76.
- the humidity sensor 73, the heating element 72, the body 74 and the housing 75 are pressed against each other in the present embodiment, wherein the housing 75 and the body 74 are screwed together to ensure a constant contact pressure.
- This compression ensures that the volume 71 is particularly dense. So can be effectively avoided that settles water with a much higher thermal conductivity in the other volume and causes a thermal short circuit.
- the described compression of the housing 75, the body 74, the heating element 72 and the humidity sensor 73 is provided instead of the bond. Otherwise, the adhesive in the area of the opening 79 is prevented from diffusing or evaporating into the volume 71 and influencing the measurements.
- the thermally conductive body 74 forms a heat or cold storage whose internal temperature remains approximately equal. Neither influences of the person operating the sensor device nor of the person whose skin moisture is measured, nor the required heating by the heating element 72, have significant effects on the temperature of the conductive body 74.
- the housing 75 itself has no significant thermal conductivity and heat capacity. Since the housing 75 touches the heating element 72 and the humidity sensor 73 only at a few points, and the further volume 77 filled with air is formed between the housing 75, the heating element 72 and the humidity sensor 73, it occurs between the housing 75 and the heating element 72 or the humidity sensor 73 only to low thermal influences.
- the humidity sensor 73 and the volume 71 can be kept at a constant temperature by the heating element 72 designed as a Peltier element, whereby the influence of the temperature on the measurement is only slightly influenced.
- a temperature sensor is arranged, by means of whose measured value the activation of the heating element 72 takes place and the temperature is constant is held.
- an il empeiaiuiieyeiuiui duu i should be omitted.
- the housing 75 is connected to a control unit, not shown, with a handle.
- the operating device has a display and the control unit connected to the terminals 82, 83 of the heating element 72 and the humidity sensor 73. Furthermore, a trigger button for initiating the measurement is available.
- FIG. 36 shows the cleaning and disinfection of a sensor according to the invention.
- the sensor is integrated in a housing as shown in FIG. 35.
- the sensor shown in Fig. 35 is placed in a container 270 and sealed airtight.
- the container 270 is partially filled with water 272.
- the sensor protrudes from above into the container 270.
- a heating element 271 At the bottom of the container is a heating element 271, in this case, a heating plate.
- the heating element 271 is activated, the water 272 is heated to a predetermined temperature through the container 270 so that bacteria on the sensor are killed.
- the heating element 271 is activated, the water 272 is heated to a predetermined temperature through the container 270 so that bacteria on the sensor are killed.
- the water is heated to temperatures of 61.5 ° C for about half an hour.
- the water 272 is heated to 80 ° C for half an hour.
- the water 272 is heated to about 100 ° C for five to thirty minutes.
- Bacillus anthracis spores can be killed at temperatures of 105 ° C after 5 minutes of application.
- water 272 is heated to 105 ° C for 15 minutes.
- the water 272 is heated to 132 ° C for 60 minutes. Of course, a higher temperature and a longer disinfection time can be set to kill the bacteria.
- the sensor itself In order to transport the residual moisture from the sensor, the sensor itself is heated by means of the heating element 273 outside the container 272 and dried.
- cover caps or protective caps or hygiene caps can be used in all embodiments of the invention.
- These protective caps are placed over the sensor and prevent direct contact of the object to be measured, such as the human or animal skin, with the moisture-sensitive surface of the sensor.
- the sensor is protected by the cap or protective cap effectively against contamination and also from damage.
- the Cover caps contain a permeable section that lets water vapor through to the sensor. This permeable portion may be formed by PTFE plastic, porous silicone rubber or braided stainless steel wires.
- PTFE plastic porous silicone rubber or braided stainless steel wires.
- the vapor released from the human skin contains the person to be measured, depending on the diet and pathology.
- methanol can be released through the skin through alcohol consumption.
- a protective cap can be used effectively.
- the therapeutically active substance is in a carrier, for example in a sticky patch or in a cream.
- the permeability of the skin can be determined by a simplified method by measuring the moisture of the skin.
- the moisture released by the skin water vapor rate
- the more moisture that evaporates from the skin the more permeable the skin is. If the skin is permeable, the medication will be absorbed faster and for a short period of time. If the skin is less permeable, the medication will be slower and absorbed over a longer period of time.
- further substances can be added to the carrier or the medicament which accelerate or slow down the delivery of the medicament and thus compensate for the effects of the different permeability of the skin.
- Accelerated absorption of drugs through a more permeable skin can be compensated by the addition of substances that slow the delivery of the drug. Conversely, the addition of substances which accelerate the delivery of the drug may compensate for the effects of less permeable skin.
- a preferred example of application of this method is the delivery of nicotine for smoking cessation, but generally the dosage of any skin-administrable drug can be adjusted by the following procedure. Before the administration of the drug to the person to be treated is the
- the skin moisture is determined as an indicator of the permeability of the skin and the uptake of the drug after a standardized administration is determined, for example by taking and examining a blood sample, urine sample, or the like. Subsequently, the skin moisture or permeability and the absorbed drug dose are correlated with each other, whereby a relationship between skin moisture and absorbed drug dose, possibly over time, is determined. This measurement is carried out with different carriers which deliver the therapeutically active substance at different speeds.
- the method can be used for metered delivery of all substances that can be absorbed through the skin.
- the skin moisture or permeability of the person's skin is first determined.
- that carrier is selected which delivers the therapeutically active substance to the person in a therapeutically defined period of time.
- the period of delivery may be determined by selecting the carrier, with different carriers containing different adjuvants that delay or accelerate the delivery of the drug.
- the dose of the drug or therapeutic substance can be increased by applying the carrier with the drug in a larger surface area of the skin.
- all medicaments which can be absorbed via the skin can be used as the ingredients to be administered, especially therapeutic ingredients.
- Particularly advantageous is the use of antibiotics, steroids, hormones such as estrogens, nicotine, proteins such as insulin, liposomes, capsaicin to numb the skin, etc.
- any antibiotics such as estrogens, nicotine, proteins such as insulin, liposomes, capsaicin to numb the skin, etc.
- Humidity sensor can be used.
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Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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ATA1723/2009A AT508976B1 (de) | 2009-10-30 | 2009-10-30 | Feuchtigkeitssensor |
AT20552009A AT508940B1 (de) | 2009-12-30 | 2009-12-30 | Sensorvorrichtung |
PCT/AT2010/000411 WO2011050381A1 (de) | 2009-10-30 | 2010-10-29 | Feuchtigkeitssensor |
Publications (1)
Publication Number | Publication Date |
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EP2494344A1 true EP2494344A1 (de) | 2012-09-05 |
Family
ID=43708726
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
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EP10787257A Withdrawn EP2494343A2 (de) | 2009-10-30 | 2010-10-29 | Sensorvorrichtung |
EP10795907A Withdrawn EP2494344A1 (de) | 2009-10-30 | 2010-10-29 | Feuchtigkeitssensor |
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EP10787257A Withdrawn EP2494343A2 (de) | 2009-10-30 | 2010-10-29 | Sensorvorrichtung |
Country Status (3)
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US (1) | US8869596B2 (de) |
EP (2) | EP2494343A2 (de) |
WO (2) | WO2011050381A1 (de) |
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US9989267B2 (en) * | 2012-02-10 | 2018-06-05 | Gentherm Incorporated | Moisture abatement in heating operation of climate controlled systems |
DE102012103691A1 (de) * | 2012-04-26 | 2013-10-31 | Endress + Hauser Conducta Gesellschaft für Mess- und Regeltechnik mbH + Co. KG | Sensor zur Messung der Leitfähigkeit |
DE102012017205A1 (de) * | 2012-08-31 | 2014-03-27 | Fresenius Medical Care Deutschland Gmbh | Verfahren und Vorrichtung zum Prüfen von auf die Haut eines Patienten aufzubringenden Sensoren zum Erkennen von Flüssigkeit oder Feuchtigkeit |
JP6652493B2 (ja) | 2014-02-14 | 2020-02-26 | ジェンサーム インコーポレイテッドGentherm Incorporated | 伝導性および対流性の温度調節シート |
US9568445B2 (en) * | 2014-04-09 | 2017-02-14 | International Business Machines Corporation | Salt-based device and a circuit to monitor and log the times a data center air goes above a predefined limit |
US11639816B2 (en) | 2014-11-14 | 2023-05-02 | Gentherm Incorporated | Heating and cooling technologies including temperature regulating pad wrap and technologies with liquid system |
WO2016077843A1 (en) | 2014-11-14 | 2016-05-19 | Cauchy Charles J | Heating and cooling technologies |
US11857004B2 (en) | 2014-11-14 | 2024-01-02 | Gentherm Incorporated | Heating and cooling technologies |
AT516999A1 (de) * | 2015-04-03 | 2016-10-15 | Vasema Diagnostics Ag | Abdeckkappe |
EP3106841B1 (de) * | 2015-06-18 | 2017-08-09 | E+E Elektronik Ges.m.b.H. | Umkapselter gassensor |
JP6499532B2 (ja) * | 2015-06-30 | 2019-04-10 | ファナック株式会社 | 吸湿剤の吸湿量を取得する機能を備えた回転エンコーダ |
DE102016005713B4 (de) * | 2016-05-12 | 2019-08-14 | Drägerwerk AG & Co. KGaA | Medizinische Einrichtung und Verfahren zur Überwachung der Reinigung von dessen Oberfläche |
US10816498B2 (en) | 2017-05-30 | 2020-10-27 | Raymond Hoheisel | Humidity sensor and related methods |
CN108627536B (zh) * | 2018-04-04 | 2020-06-16 | 长安大学 | 一种浇注式导电沥青混凝土传导热效果预估方法 |
DE102018003062A1 (de) * | 2018-04-14 | 2019-10-17 | Loba Gmbh & Co. Kg | Vorrichtung zum Feststellen des Trocknungsgrades von Auftragprodukten für Fußböden und deren Beläge |
US11223004B2 (en) | 2018-07-30 | 2022-01-11 | Gentherm Incorporated | Thermoelectric device having a polymeric coating |
US11215575B2 (en) * | 2018-10-31 | 2022-01-04 | Wagner Electronic Products, Inc. | Hand held moisture meter intelligent recording |
JP7608337B2 (ja) | 2018-11-30 | 2025-01-06 | ジェンサーム インコーポレイテッド | 熱電調整システム及び方法 |
CN209326840U (zh) | 2018-12-27 | 2019-08-30 | 热敏碟公司 | 压力传感器及压力变送器 |
US11152557B2 (en) | 2019-02-20 | 2021-10-19 | Gentherm Incorporated | Thermoelectric module with integrated printed circuit board |
DE102020120111A1 (de) * | 2020-07-30 | 2022-02-03 | Dräger Safety AG & Co. KGaA | Elektronische Fußfessel und entsprechende Verfahren |
RU2758198C1 (ru) * | 2021-03-24 | 2021-10-26 | Федеральное государственное бюджетное образовательное учреждение высшего образования «Воронежский государственный университет инженерных технологий» (ФГБОУ ВО «ВГУИТ») | Способ среднеинтегральной оценки прочности связи влаги в веществе в любом заданном диапазоне влагосодержаний |
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- 2010-10-29 WO PCT/AT2010/000411 patent/WO2011050381A1/de active Application Filing
- 2010-10-29 WO PCT/AT2010/000412 patent/WO2011050382A2/de active Application Filing
- 2010-10-29 EP EP10787257A patent/EP2494343A2/de not_active Withdrawn
- 2010-10-29 EP EP10795907A patent/EP2494344A1/de not_active Withdrawn
- 2010-10-29 US US13/505,134 patent/US8869596B2/en not_active Expired - Fee Related
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Also Published As
Publication number | Publication date |
---|---|
EP2494343A2 (de) | 2012-09-05 |
US8869596B2 (en) | 2014-10-28 |
WO2011050382A2 (de) | 2011-05-05 |
US20120234078A1 (en) | 2012-09-20 |
WO2011050382A3 (de) | 2011-07-07 |
WO2011050381A1 (de) | 2011-05-05 |
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